WO2021217585A1 - 二次电池、其制备方法及含有该二次电池的装置 - Google Patents
二次电池、其制备方法及含有该二次电池的装置 Download PDFInfo
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- WO2021217585A1 WO2021217585A1 PCT/CN2020/088299 CN2020088299W WO2021217585A1 WO 2021217585 A1 WO2021217585 A1 WO 2021217585A1 CN 2020088299 W CN2020088299 W CN 2020088299W WO 2021217585 A1 WO2021217585 A1 WO 2021217585A1
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Definitions
- This application belongs to the field of electrochemical technology, and more specifically, relates to a secondary battery, a preparation method thereof, and a device containing the secondary battery.
- Secondary batteries are widely used in various consumer electronic products and electric vehicles because of their outstanding characteristics such as light weight, no pollution, and no memory effect.
- this application provides a secondary battery, a preparation method thereof, and a device containing the secondary battery, aiming to enable the secondary battery to have a higher energy density while taking into account better The low temperature rate performance and long high temperature cycle life.
- a second aspect of the present application provides a method for manufacturing a secondary battery, which includes preparing the negative pole piece of the secondary battery through the following steps:
- W 3R is the peak area of the 101 crystal plane in the X-ray diffraction spectrum of the first negative electrode active material at a diffraction angle of 43.3 ⁇ 0.05°
- W 2H is the X-ray diffraction spectrum of the first negative electrode active material at the diffraction angle The peak area of the 101 crystal plane at 44.5 ⁇ 0.05°.
- a third aspect of the present application provides a device, which includes the secondary battery described in the first aspect of the present application or a secondary battery prepared according to the method described in the second aspect of the present application.
- the negative electrode sheet of the secondary battery of the present application includes a first negative electrode film layer and a second negative electrode film layer, and the first negative electrode active material of a specific composition is selected in the first negative electrode film layer, thereby enabling the secondary Under the premise of higher energy density, the battery takes into account both better low-temperature rate performance and longer high-temperature cycle life.
- FIG. 1 is a schematic diagram of an embodiment of the secondary battery of the present application.
- FIG. 2 is a schematic diagram of an embodiment of the negative pole piece in the secondary battery of the present application.
- FIG. 3 is a schematic diagram of another embodiment of the negative pole piece in the secondary battery of the present application.
- Fig. 4 is an exploded schematic view of an embodiment of the secondary battery of the present application.
- Fig. 5 is a schematic diagram of an embodiment of a battery module.
- Fig. 6 is a schematic diagram of an embodiment of a battery pack.
- Fig. 7 is an exploded view of Fig. 6.
- FIG. 8 is a schematic diagram of an embodiment of a device in which the secondary battery of the present application is used as a power source.
- any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range.
- each individually disclosed point or single value can be used as a lower limit or upper limit in combination with any other point or single value or with other lower or upper limits to form an unspecified range.
- the first aspect of the application provides a secondary battery.
- the secondary battery includes a positive pole piece, a negative pole piece and an electrolyte.
- active ions are inserted and extracted back and forth between the positive pole piece and the negative pole piece.
- the electrolyte conducts ions between the positive pole piece and the negative pole piece.
- the negative electrode piece of the present application includes a negative electrode current collector and a negative electrode film layer.
- the negative electrode film layer includes a first negative electrode film layer and a second negative electrode film layer.
- the first negative electrode film layer is disposed on at least one surface of the negative electrode current collector.
- the second negative electrode film layer is disposed on the first negative electrode film layer and includes a second negative electrode active material;
- the second negative electrode active material includes artificial graphite; wherein, W 3R is the X-ray diffraction spectrum of the first negative electrode active material in the The peak area of the 101 crystal plane at the diffraction angle of 43.3 ⁇ 0.05°, and W 2H is the peak area of the 101 crystal plane at the diffraction angle of 44.5 ⁇ 0.05° in the X-ray diffraction spectrum of the first negative electrode active material.
- the battery can have a better low-temperature rate performance under the premise of a higher energy density.
- the inventor’s research found that when the first negative electrode active material of the present application includes natural graphite and the second negative electrode active material includes artificial graphite, and the S1 of the first negative electrode active material is controlled within the given range, the upper and lower layers of the negative electrode The active sites are reasonably matched, which is conducive to improving the rate performance of the battery; at the same time, the porosity of the upper and lower layers is also reasonably optimized, which is conducive to electrolyte infiltration and improves the cycle life of the battery.
- the first negative electrode active material satisfies 0.70 ⁇ S1 ⁇ 0.80.
- the inventor found that the negative pole piece of the present application can further improve the performance of the battery if one or more of the following parameters are optionally satisfied on the basis of the above-mentioned design.
- the graphitization degree of the first negative electrode active material is 95% to 98%, preferably 96% to 97%.
- the graphitization degree of the second negative electrode active material is 90%-95%, preferably 91%-93%.
- the powder compaction density of the first negative electrode active material under a force of 50,000 N is 1.85 g/cm 3 to 2.1 g/cm 3 , preferably 1.9 g/cm 3 to 2.0 g /cm 3 ;.
- the second negative electrode active material has a powder compaction density of 1.7 g/cm 3 to 1.9 g/cm 3 under a force of 50,000 N, preferably 1.8 g/cm 3 to 1.9 g /cm 3 .
- the specific surface area of the first anode active material is of 1.6m 2 /g ⁇ 2.4m 2 / g, preferably 1.8m 2 /g ⁇ 2.2m 2 / g.
- the specific surface area of the second cathode active material (SSA) of 0.7m 2 /g ⁇ 1.5m 2 / g, preferably 0.9m 2 /g ⁇ 1.3m 2 / g.
- the volume average particle diameter of the first anode active material V 50 D volume average particle diameter D V is greater than the second negative electrode active material 50.
- the volume average particle diameter D V 50 of the first negative electrode active material is 15 ⁇ m to 19 ⁇ m, preferably 16 ⁇ m to 18 ⁇ m.
- the volume average particle diameter D V 50 of the second negative electrode active material is 14 ⁇ m to 18 ⁇ m, preferably 15 ⁇ m to 17 ⁇ m.
- the inventor’s research found that when the volume average particle size D V 50 of the first negative electrode active material and/or the second negative electrode active material is within the given range, it helps to further improve the dynamic performance of the battery; at the same time, the particle size is within the range Within the given range, the difference in capacity of the upper and lower active materials can also be reduced, and the risk of lithium evolution during the battery cycle can be reduced, thereby further improving the cycle performance of the battery.
- the morphology of the natural graphite is one or more of spherical and quasi-spherical.
- the morphology of the artificial graphite is one or more of a block shape and a sheet shape.
- the mass ratio of the natural graphite in the first negative electrode active material is ⁇ 50%, more preferably 80%-100%.
- the mass ratio of the artificial graphite in the second negative electrode active material is ⁇ 80%, more preferably 90%-100%.
- W 2H and W 3R are well known in the art and can be tested by methods known in the art. For example, it can be tested by using an X-ray diffractometer (such as Bruker D8 Discover). Then, the value of S1 can be calculated by the formula of this application.
- the degree of graphitization of the material has a well-known meaning in the art, and can be tested using methods known in the art.
- an X-ray diffractometer (Bruker D8 Discover) can be used to test.
- the D V 50 of the material has a well-known meaning in the art, and can be tested using methods known in the art.
- a laser diffraction particle size distribution measuring instrument such as Mastersizer 3000
- the particle size distribution laser diffraction method for details, please refer to GB/T19077-2016
- Dv50 refers to the particle size when the cumulative volume percentage of the material reaches 50%.
- the powder compaction density of the material has the meaning known in the art, and can be tested by methods known in the art.
- an electronic pressure testing machine such as UTM7305
- the pressure is set to 50000N.
- the specific surface area (SSA) of the material has a well-known meaning in the art, and can be tested by methods known in the art, for example, it can be tested by the nitrogen adsorption specific surface area analysis test method, and the BET (Brunauer Emmett Calculated by Teller) method, wherein the nitrogen adsorption specific surface area analysis test can be performed by the NOVA 2000e specific surface area and pore size analyzer of Kanta Corporation of the United States.
- the morphology of the negative electrode active material has a well-known meaning in the art, and can be tested by a method known in the art.
- the extremely active material is glued to the conductive adhesive, and the morphology of the particles is tested using a scanning electron microscope (such as sigma300). The test can refer to JY/T010-1996.
- test sample is taken from the negative electrode film after cold pressing, as an example, the sample can be taken as follows:
- an optical microscope or a scanning electron microscope can be used to assist in determining the position of the boundary between the first negative electrode film layer and the second negative electrode film layer.
- the thickness of the negative electrode film layer is preferably ⁇ 60 ⁇ m, more preferably 65 ⁇ m to 80 ⁇ m. It should be noted that the thickness of the negative electrode film layer refers to the total thickness of the negative electrode film layer (that is, the sum of the thicknesses of the first negative electrode film layer and the second negative electrode film layer).
- the areal density of the negative electrode film layer is 10 mg/cm 2 ⁇ CW ⁇ 13 mg/cm 2 , preferably, 10.5 mg/cm 2 ⁇ CW ⁇ 11.5 mg/cm 2 . It should be noted that the areal density of the negative electrode film layer refers to the areal density of the entire negative electrode film layer (that is, the sum of the areal densities of the first negative electrode film layer and the second negative electrode film layer).
- the thickness ratio of the first negative electrode film layer to the second negative electrode film layer is 1:1.01 to 1:1.1, preferably 1:1.02 to 1:1.06.
- the thickness of the upper and lower layers is in the given range, it is beneficial to form a gradient pore distribution in the upper and lower layers, so that the liquid phase conduction resistance of the active ions from the positive electrode on the surface of the negative electrode film layer is reduced, and the accumulation of ions on the surface layer will not cause the problem of lithium evolution.
- the uniform diffusion of active ions in the membrane layer is beneficial to reduce polarization and further improve the dynamic performance and cycle performance of the battery.
- the thickness of the negative electrode film layer can be measured by a ten-meter ruler, for example, it can be measured by a ten-meter ruler with a model of Mitutoyo293-100 and an accuracy of 0.1 as t.
- each of the first negative electrode film layer and the second negative electrode film layer can be tested by using a scanning electron microscope (such as ZEISS Sigma 300).
- the sample preparation is as follows: firstly, the negative pole piece is cut into a sample to be tested of a certain size (for example, 2cm ⁇ 2cm), and the negative pole piece is fixed on the sample table by paraffin wax.
- sample stage into the sample rack, lock and fix it, turn on the power of the argon ion cross-section polisher (such as IB-19500CP) and vacuum (such as 10 -4 Pa), set the argon flow (such as 0.15 MPa) and voltage (such as 8KV) and polishing time (for example, 2 hours), adjust the sample stage to swing mode to start polishing.
- the power of the argon ion cross-section polisher such as IB-19500CP
- vacuum such as 10 -4 Pa
- argon flow such as 0.15 MPa
- voltage such as 8KV
- polishing time for example, 2 hours
- the average value of the test results of a plurality of test areas is taken as the average value of the thickness of the first negative electrode film layer and the second negative electrode film layer.
- the areal density of the negative electrode film layer has a well-known meaning in the art, and can be tested by a method known in the art. For example, take a negative electrode piece coated on one side and cold pressed (if it is a negative electrode piece coated on both sides, wipe off the negative electrode film on one side first), die cut into a small wafer with an area of S1, and weigh Its weight is recorded as M1. Then wipe off the negative electrode film of the above-mentioned weighed negative electrode sheet, weigh the weight of the negative electrode current collector, and record it as M0.
- the area density of the negative electrode film layer (weight of the negative electrode sheet M1-weight of the negative electrode current collector M0 )/S1.
- multiple groups for example, 10 groups) of samples to be tested can be tested, and the average value can be calculated as the test result.
- the negative electrode current collector can be a metal foil or a composite current collector (a metal material can be arranged on a polymer substrate to form a composite current collector).
- a metal material can be arranged on a polymer substrate to form a composite current collector.
- copper foil may be used as the negative electrode current collector.
- the first negative electrode film layer and/or the second negative electrode film layer usually include a negative electrode active material, an optional binder, an optional conductive agent, and other optional auxiliary agents, It is usually formed by coating and drying the negative electrode film slurry.
- the negative electrode film slurry coating is usually formed by dispersing the negative electrode active material and optional conductive agent and binder in a solvent and stirring uniformly.
- the solvent can be N-methylpyrrolidone (NMP) or deionized water, for example.
- Other optional additives can be, for example, thickening and dispersing agents (such as sodium carboxymethyl cellulose CMC-Na), PTC thermistor materials, and the like.
- the conductive agent may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
- the binder may include styrene-butadiene rubber (SBR), water-based acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer One or more of (EVA), polyvinyl alcohol (PVA) and polyvinyl butyral (PVB).
- SBR styrene-butadiene rubber
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- EVA ethylene-vinyl acetate copolymer
- EVA polyvinyl alcohol
- PVB polyvinyl butyral
- the first negative electrode active material and/or the second negative electrode active material may optionally include a certain amount of other commonly used negative electrode active materials in addition to the aforementioned negative electrode active material of the present application, For example, one or more of soft carbon, hard carbon, silicon-based materials, tin-based materials, and lithium titanate.
- the silicon-based material can be selected from one or more of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, and silicon alloys.
- the tin-based material can be selected from one or more of elemental tin, tin oxide compounds, and tin alloys. The preparation methods of these materials are well known and can be obtained commercially. Those skilled in the art can make an appropriate choice according to the actual use environment.
- the negative electrode film layer can be provided on one surface of the negative electrode current collector, or can be provided on both surfaces of the negative electrode current collector at the same time.
- FIG. 2 shows a schematic diagram of an embodiment of the negative pole piece 10 of the present application.
- the negative electrode piece 10 is composed of a negative electrode current collector 101, a first negative electrode film layer 103 respectively disposed on both surfaces of the negative electrode current collector, and a second negative electrode film layer 102 disposed on the first negative electrode film layer 103.
- FIG. 3 shows a schematic diagram of another embodiment of the negative pole piece 10 of the present application.
- the negative electrode piece 10 is composed of a negative electrode current collector 101, a first negative electrode film layer 103 disposed on one surface of the negative electrode current collector, and a second negative electrode film layer 102 disposed on the first negative electrode film layer 103.
- each negative electrode film (such as film thickness, areal density, etc.) given in this application all refer to the parameter range of a single-sided film.
- the film layer parameters on any one of the surfaces meet the requirements of the present application, which is considered to fall within the protection scope of the present application.
- the ranges of film thickness, areal density and the like mentioned in this application all refer to the film parameters after being compacted by cold pressing and used for assembling the battery.
- the negative electrode sheet does not exclude additional functional layers other than the negative electrode film layer.
- the negative pole piece described in the present application further includes a conductive primer layer (for example, composed of a conductive agent and a binder) sandwiched between the current collector and the first film layer and arranged on the surface of the current collector. ).
- the negative pole piece described in the present application further includes a protective covering layer covering the surface of the second film layer.
- the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector and including a positive electrode active material.
- the positive electrode current collector has two opposite surfaces in its thickness direction, and the positive electrode film layer may be laminated on either or both of the two opposite surfaces of the positive electrode current collector.
- the positive electrode current collector can be a conventional metal foil or a composite current collector (a metal material can be arranged on a polymer substrate to form a composite current collector).
- a metal material can be arranged on a polymer substrate to form a composite current collector.
- aluminum foil may be used as the positive electrode current collector.
- the positive electrode active material may include one or more of lithium transition metal oxides, lithium-containing phosphates with an olivine structure, and their respective modified compounds.
- lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide One or more of the compounds, lithium nickel cobalt aluminum oxide and its modified compounds.
- lithium-containing phosphates with an olivine structure may include, but are not limited to, lithium iron phosphate, lithium iron phosphate and carbon composite material, lithium manganese phosphate, lithium manganese phosphate and carbon composite material, lithium iron manganese phosphate, lithium iron manganese phosphate
- One or more of the composite materials with carbon and its modified compounds may be used. The present application is not limited to these materials, and other conventionally known materials that can be used as positive electrode active materials for secondary batteries can also be used.
- the positive electrode active material may include one or more of the lithium transition metal oxide and its modified compounds shown in Formula 1.
- M is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn 0.5 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 1, 1 ⁇ e ⁇ 2, 0 ⁇ f ⁇ 1, M is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Cu, Cr, Mg, Fe, V, Ti and B
- A is selected from one or more of N, F, S and Cl.
- the modification compound of each of the above-mentioned materials may be doping modification and/or surface coating modification of the material.
- the positive electrode film layer may optionally include a binder and/or a conductive agent.
- the binder used for the positive electrode film layer may include one or more of polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- the conductive agent used for the positive electrode film layer may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
- the electrolyte conducts ions between the positive pole piece and the negative pole piece.
- the type of electrolyte in this application can be selected according to requirements.
- the electrolyte may be selected from at least one of solid electrolytes and liquid electrolytes (ie, electrolytes).
- an electrolyte is used as the electrolyte.
- the electrolyte includes electrolyte salt and solvent.
- the electrolyte salt can be selected from LiPF 6 (lithium hexafluorophosphate), LiBF 4 (lithium tetrafluoroborate), LiClO 4 (lithium perchlorate), LiAsF 6 (lithium hexafluoroarsenate), LiFSI (bisfluorosulfonate) Lithium imide), LiTFSI (lithium bistrifluoromethanesulfonimide), LiTFS (lithium trifluoromethanesulfonate), LiDFOB (lithium difluorooxalate), LiBOB (lithium bisoxalate), LiPO 2 F 2 (Lithium difluorophosphate), LiDFOP (lithium difluorodioxalate phosphate) and LiTFOP (lithium tetrafluorooxalate phosphate) one or more.
- LiPF 6 lithium hexafluorophosphate
- LiBF 4 lithium tetrafluoroborate
- the solvent may be selected from ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethylene propyl carbonate (EPC), butylene carbonate (BC), fluoroethylene carbonate (FEC), methyl formate (MF), methyl acetate Ester (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB) , Ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), methyl ethyl sulfone (EMS) and diethyl sulfone (ESE) one
- the electrolyte may also optionally include additives.
- the additives can include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery performance, such as additives that improve battery overcharge performance, additives that improve battery high-temperature performance, and battery low-temperature performance. Additives, etc.
- the isolation film is arranged between the positive pole piece and the negative pole piece to play a role of isolation.
- the type of isolation membrane in this application, and any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be selected.
- the material of the isolation membrane can be selected from one or more of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride.
- the isolation film can be a single-layer film or a multilayer composite film. When the isolation film is a multilayer composite film, the materials of each layer can be the same or different.
- the positive pole piece, the negative pole piece, and the separator can be made into an electrode assembly through a winding process or a lamination process.
- the secondary battery may include an outer package.
- the outer packaging can be used to encapsulate the above-mentioned electrode assembly and electrolyte.
- the outer packaging of the secondary battery may be a hard case, such as a hard plastic case, aluminum case, steel case, or the like.
- the outer packaging of the secondary battery may also be a soft bag, such as a pouch type soft bag.
- the material of the soft bag can be plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), and the like.
- FIG. 1 shows a secondary battery 5 of a square structure as an example.
- the outer package may include a housing 51 and a cover 53.
- the housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
- the housing 51 has an opening communicating with the accommodating cavity, and a cover plate 53 can cover the opening to close the accommodating cavity.
- the positive pole piece, the negative pole piece, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process.
- the electrode assembly 52 is packaged in the accommodating cavity.
- the electrolyte is infiltrated in the electrode assembly 52.
- the number of electrode assemblies 52 included in the secondary battery 5 can be one or several, which can be adjusted according to requirements.
- the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
- Fig. 5 is a battery module 4 as an example.
- a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other manner. Furthermore, the plurality of secondary batteries 5 can be fixed by fasteners.
- the battery module 4 may further include a housing having an accommodating space, and a plurality of secondary batteries 5 are accommodated in the accommodating space.
- the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
- the battery pack 1 may include a battery box and a plurality of battery modules 4 provided in the battery box.
- the battery box includes an upper box body 2 and a lower box body 3.
- the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4.
- a plurality of battery modules 4 can be arranged in the battery box in any manner.
- a method for preparing a secondary battery which includes preparing the negative pole piece of the secondary battery through the following steps:
- W 3R is the peak area of the 101 crystal plane in the X-ray diffraction spectrum of the first negative electrode active material at a diffraction angle of 43.3 ⁇ 0.05°
- W 2H is the X-ray diffraction spectrum of the first negative electrode active material at the diffraction angle The peak area of the 101 crystal plane at 44.5 ⁇ 0.05°.
- the secondary battery of the present application can be made under the premise of higher energy density. , At the same time, good low temperature rate performance and long cycle life are taken into account.
- the first negative electrode active material slurry and the second negative electrode active material slurry may be applied at the same time at one time, or may be applied in two separate steps.
- the first negative active material slurry and the second negative active material slurry are simultaneously coated at one time. Coating at the same time can make the adhesion between the upper and lower negative film layers better, which helps to further improve the cycle performance of the battery.
- the positive pole piece of the present application can be prepared as follows: the positive electrode active material, optional conductive agent (such as carbon black and other carbon materials), binder (such as PVDF), etc. are mixed and dispersed in a solvent (such as NMP) In the process, after stirring, it is coated on the positive electrode current collector, and the positive electrode piece is obtained after drying. Materials such as metal foil such as aluminum foil or porous metal plate can be used as the positive electrode current collector.
- the positive electrode tab can be obtained by punching or laser die cutting in the uncoated area of the positive electrode current collector.
- the third aspect of the present application provides a device.
- the device includes the secondary battery of the first aspect of the present application or the secondary battery prepared according to the method of the second aspect of the present application.
- the secondary battery can be used as a power source of the device, and can also be used as an energy storage unit of the device.
- the device of the present application uses the secondary battery provided by the present application, and therefore has at least the same advantages as the secondary battery.
- the device can be, but is not limited to, mobile devices (such as mobile phones, laptop computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf Vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
- mobile devices such as mobile phones, laptop computers, etc.
- electric vehicles such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf Vehicles, electric trucks, etc.
- electric trains ships and satellites, energy storage systems, etc.
- the device can select a secondary battery, a battery module, or a battery pack according to its usage requirements.
- Fig. 8 is a device as an example.
- the device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
- a battery pack or a battery module can be used.
- the device may be a mobile phone, a tablet computer, a notebook computer, and the like.
- the device is generally required to be thin and light, and a secondary battery can be used as a power source.
- the first step is to prepare negative electrode slurry 1: the first negative electrode active material natural graphite, binder SBR, thickener sodium carboxymethyl cellulose (CMC-Na) and conductive carbon black (Super P) are weighed to The weight ratio of 96.2:1.8:1.2:0.8 and deionized water are added to the stirring tank in a certain order and mixed to prepare negative electrode slurry 1.
- the first negative electrode active material natural graphite, binder SBR, thickener sodium carboxymethyl cellulose (CMC-Na) and conductive carbon black (Super P) are weighed to The weight ratio of 96.2:1.8:1.2:0.8 and deionized water are added to the stirring tank in a certain order and mixed to prepare negative electrode slurry 1.
- the second step is to prepare negative electrode slurry 2: the second negative electrode active material artificial graphite, binder SBR, thickener sodium carboxymethyl cellulose (CMC-Na) and conductive carbon black (Super P) are weighed to The weight ratio of 96.2:1.8:1.2:0.8 and deionized water are added to the stirring tank in a certain order and mixed to prepare negative electrode slurry 2.
- the second negative electrode active material artificial graphite, binder SBR, thickener sodium carboxymethyl cellulose (CMC-Na) and conductive carbon black (Super P) are weighed to The weight ratio of 96.2:1.8:1.2:0.8 and deionized water are added to the stirring tank in a certain order and mixed to prepare negative electrode slurry 2.
- the negative electrode slurry 1 and the negative electrode slurry 2 are simultaneously extruded through a dual-cavity coating device.
- the negative electrode slurry 1 is coated on the negative electrode current collector to form a first negative electrode film layer
- the negative electrode slurry 2 is coated on the first negative electrode film layer to form a second negative electrode film layer;
- the mass ratio is 1:1; the areal density of the negative electrode film layer is 11.5 mg/cm 2 ; the compacted density of the negative electrode film layer is 1.65 g/cm 3 .
- the coated wet film is baked in an oven through different temperature zones to obtain dry pole pieces, and then cold-pressed to obtain the required negative electrode film layer, and then to obtain negative pole pieces through processes such as slitting and cutting.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- DEC diethyl carbonate
- the batteries of the examples and comparative examples were subjected to charge and discharge tests, and a discharge current of 1.0C (that is, the current value at which the theoretical capacity was completely discharged within 1h) was discharged at a constant current to a cut-off voltage of 2.8V . Then charge with a constant current of 1.0C until the charge cut-off voltage is 4.2V, and continue constant voltage charging until the current is 0.05C. At this time, the battery is in a fully charged state. After the fully charged battery is allowed to stand for 5 minutes, discharge at a constant current of 1.0C to the discharge cut-off voltage. The discharge capacity at this time is the actual capacity of the battery at 1.0C, denoted as C0.
- the batteries of each embodiment and comparative example were prepared according to the above methods, and various performance parameters were measured. The results are shown in Table 1 to Table 2 below.
- the volume average particle size D V 50 of natural graphite and artificial graphite also has a greater impact on battery performance.
- the volume average particle size D V 50 of natural graphite is preferably in the range of 15 ⁇ m to 19 ⁇ m, more preferably 16 ⁇ m Within the range of ⁇ 18 ⁇ m; the volume average particle diameter D V 50 of the artificial graphite is preferably within the range of 14 ⁇ m to 18 ⁇ m, more preferably within the range of 15 ⁇ m to 17 ⁇ m.
- the secondary battery in order to maintain the secondary battery with a higher energy density, while taking into account better low-temperature rate performance and longer cycle life, the secondary battery should meet 0.60 ⁇ S1 ⁇ 0.85.
Abstract
Description
Claims (14)
- 一种二次电池,包括负极极片,所述负极极片包括负极集流体及负极膜层,所述负极膜层包括第一负极膜层和第二负极膜层,所述第一负极膜层设置在负极集流体至少一个表面上且包括第一负极活性材料,所述第二负极膜层设置在第一负极膜层上且包括第二负极活性材料;所述第一负极活性材料包括天然石墨,且所述第一负极活性材料满足:0.60≤S1≤0.85,其中S1=W 2H/(W 3R+W 2H);所述第二负极活性材料包括人造石墨;其中,W 3R为第一负极活性材料的X射线衍射谱图中在衍射角43.3±0.05°时101晶面的峰面积,W 2H为第一负极活性材料的X射线衍射谱图中在衍射角44.5±0.05°时101晶面的峰面积。
- 根据权利要求1所述的二次电池,其特征在于:0.70≤S1≤0.80。
- 根据权利要求1至2任一项所述的二次电池,其特征在于:所述第一负极活性材料的体积平均粒径D V50大于所述第二负极活性材料的体积平均粒径D V50。
- 根据权利要求1至3任一项所述的二次电池,其特征在于:所述第一负极活性材料的体积平均粒径D V50为15μm~19μm,优选为16μm~18μm;和/或,所述第二负极活性材料的体积平均粒径D V50为14μm~18μm,优选为15μm~17μm。
- 根据权利要求1至4任一项所述的二次电池,其特征在于:所述第一负极活性材料的石墨化度为95%~98%,优选为96%~97%;和/或,所述第二负极活性材料的石墨化度为90%~95%,优选为91%~93%。
- 根据权利要求1至5任一项所述的二次电池,其中,所述第一负极活性材料在50000N压力下的粉体压实密度为1.85g/cm 3~2.1g/cm 3,优选为1.9g/cm 3~2.0g/cm 3;和/或,所述第二负极活性材料在50000N压力下的粉体压实密度为1.7g/cm 3~1.9g/cm 3,优选为1.8g/cm 3~1.9g/cm 3。
- 根据权利要求1至6任一项所述的二次电池,其中,所述第一负极活性 材料的比表面积(SSA)为1.6m 2/g~2.4m 2/g,优选为1.8m 2/g~2.2m 2/g;和/或,所述第二负极活性材料的比表面积(SSA)为0.7m 2/g~1.5m 2/g,优选为0.9m 2/g~1.3m 2/g。
- 根据权利要求1至7任一项所述的二次电池,其特征在于:所述天然石墨的形貌为球形及类球形中的一种或几种;和/或,所述人造石墨的形貌为块状及片状中的一种或几种。
- 根据权利要求1至8任一项所述的二次电池,其特征在于:所述天然石墨在所述第一负极活性材料中的质量占比≥50%,优选为80%~100%;和/或,所述人造石墨在所述第二负极活性材料中的质量占比≥80%,优选为90%~100%。
- 根据权利要求1至9任一项所述的二次电池,其特征在于:所述第一负极膜层与所述第二负极膜层的厚度比为1:1.01~1:1.1,优选为1:1.02~1:1.06。
- 根据权利要求1至10任一项所述的二次电池,其特征在于:所述负极膜层的面密度CW满足:10mg/cm 2≤CW≤13mg/cm 2,优选地,10.5mg/cm 2≤CW≤11.5mg/cm 2。
- 根据权利要求1至11任一项所述的二次电池,其中,所述二次电池包括正极极片,所述正极极片包括正极集流体以及设置在正极集流体至少一个表面上且包括正极活性材料的正极膜层,所述正极活性材料包括锂过渡金属氧化物、橄榄石结构的含锂磷酸盐及其各自改性化合物中的一种或几种;优选地,所述正极活性材料包括式1所示的锂过渡金属氧化物及其改性化合物中的一种或几种,Li aNi bCo cM dO eA f 式1,所述式1中,0.8≤a≤1.2,0.5≤b<1,0<c<1,0<d<1,1≤e≤2,0≤f≤1,M选自Mn、Al、Zr、Zn、Cu、Cr、Mg、Fe、V、Ti及B中的一种或几种,A选自N、F、S及Cl中的一种或几种。
- 一种二次电池的制造方法,包括通过如下步骤制备所述二次电池的负极极片:1)在负极集流体至少一个表面上形成包括第一负极活性材料的第一负极膜层,所述第一负极活性材料包括天然石墨,且所述第一负极活性材料满足:0.60 ≤S1≤0.85,其中S1=W 2H/(W 3R+W 2H);以及2)在所述第一负极膜层上形成包括第二负极活性材料的第二负极膜层,所述第二负极活性材料包括人造石墨;其中,W 3R为第一负极活性材料的X射线衍射谱图中在衍射角43.3±0.05°时101晶面的峰面积,W 2H为第一负极活性材料的X射线衍射谱图中在衍射角44.5±0.05°时101晶面的峰面积。
- 一种装置,其特征在于:包括权利要求1至12中任一项所述的二次电池或根据权利要求13所述方法制备的二次电池。
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- 2020-04-30 EP EP20932863.2A patent/EP3958352B1/en active Active
- 2020-04-30 JP JP2022532138A patent/JP7428800B2/ja active Active
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2021
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JP2023504472A (ja) | 2023-02-03 |
KR20220092941A (ko) | 2022-07-04 |
CN113875048B (zh) | 2024-01-23 |
US20220102710A1 (en) | 2022-03-31 |
EP3958352B1 (en) | 2023-01-25 |
EP3958352A1 (en) | 2022-02-23 |
CN113875048A (zh) | 2021-12-31 |
JP7428800B2 (ja) | 2024-02-06 |
EP3958352A4 (en) | 2022-08-10 |
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